CN105646551A - Trivalent gold complex and application thereof to hydrogen manufacturing through photocatalytic reduction water - Google Patents
Trivalent gold complex and application thereof to hydrogen manufacturing through photocatalytic reduction water Download PDFInfo
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- CN105646551A CN105646551A CN201610042077.4A CN201610042077A CN105646551A CN 105646551 A CN105646551 A CN 105646551A CN 201610042077 A CN201610042077 A CN 201610042077A CN 105646551 A CN105646551 A CN 105646551A
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- Prior art keywords
- gold complex
- trivalent gold
- trivalent
- dichloromethane
- complex
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- 239000010931 gold Substances 0.000 title claims abstract description 52
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000001257 hydrogen Substances 0.000 title claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- YQTWDIVARPPQGF-UHFFFAOYSA-N [Au+3].[Cl+] Chemical compound [Au+3].[Cl+] YQTWDIVARPPQGF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- PJUOHDQXFNPPRF-UHFFFAOYSA-N 2,6-diphenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=N1 PJUOHDQXFNPPRF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 238000007445 Chromatographic isolation Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- RHXQSMVSBYAGQV-UHFFFAOYSA-N 2-(4-tert-butylphenyl)pyridine Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=CC=CC=N1 RHXQSMVSBYAGQV-UHFFFAOYSA-N 0.000 claims description 4
- NAMCOZJTWRDYSB-UHFFFAOYSA-N 3,6-ditert-butyl-9-(4-ethynylphenyl)carbazole Chemical compound C12=CC=C(C(C)(C)C)C=C2C2=CC(C(C)(C)C)=CC=C2N1C1=CC=C(C#C)C=C1 NAMCOZJTWRDYSB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- CIZQJNYFOIFDQA-UHFFFAOYSA-N 1-butyl-9-(4-ethynylphenyl)carbazole Chemical group C(CCC)C1=CC=CC=2C3=CC=CC=C3N(C1=2)C1=CC=C(C=C1)C#C CIZQJNYFOIFDQA-UHFFFAOYSA-N 0.000 abstract 1
- HTGFIWUADVBAPF-UHFFFAOYSA-N 2,6-bis(4-tert-butylphenyl)pyridine Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=CC=CC(C=2C=CC(=CC=2)C(C)(C)C)=N1 HTGFIWUADVBAPF-UHFFFAOYSA-N 0.000 abstract 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000004364 calculation method Methods 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2286—Alkynes, e.g. acetylides
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/18—Gold
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a trivalent gold complex. The general chemical formula of the trivalent gold complex is MAuL, wherein M refers to 2,6-diphenyl pyridine or 2,6-bis(4-tertiary butyl phenyl) pyridine, L refers to phenylacetylene or 3,6-2-tertiary butyl-9-(4-acetenyl phenyl)-9H-carbazole. A preparation method comprises the steps that a chlorine gold (III) precursor and L are dissolved in a mixed solution formed by cuprous iodide, dichloromethane and triethylamine, stirring is carried out for 6 h to 12 h at room temperature, and after the reaction is finished, the reaction product is purified to obtain the trivalent gold complex. The trivalent gold complex achieves visible-light responses, and is a catalyst capable of fast reducing water to prepare hydrogen.
Description
Technical field
The present invention relates to a kind of trivalent gold complex, belong to photocatalyst technology field.
Background technology
The development of society depends on traditional fossil energy, and the application of fossil energy has promoted the development of society, but resource is exhausting day by day; The uncontrolled use of fossil energy, causes serious environmental pollution and weather variation issue simultaneously. Develop reproducible new forms of energy and become the emphasis that the mankind pay close attention to.
Solar energy has the feature of use general, harmless, permanent, is considered 21 century the most potential clean energy resource. Can hydrogen use as fuel, essentially consists in process for making hydrogen. In the mode of all production hydrogen, electrolysis water can carry out large-scale production and prepare hydrogen. But, the hydrogen atom in hydrone combines closely, needs to consume very big energy during electrolysis, more than the energy that hydrogen burning itself produces. It is utilize luminous energy to make water decomposition that photochemical catalyzing prepares hydrogen, converts solar energy into chemical energy. But traditional semiconductor light-catalyst has absorption visible ray ability, catalytic rate is feature slowly. Find photocatalyst reductive water of good performance and prepare hydrogen, it is possible to resolve energy problem. In view of the above circumstances, exploitation has visible light-responded, it is possible to the catalyst that water reduction is quickly prepared hydrogen becomes the focus instantly studied.
Summary of the invention
Present invention aim to address the deficiencies in the prior art, it is provided that a kind of trivalent gold complex, it has visible light-responded, is a kind of catalyst that water reduction can quickly be prepared hydrogen.
Another object of the present invention also resides in the preparation method providing described trivalent gold complex.
Technical scheme
A kind of trivalent gold complex, its chemical general formula is MAuL, and wherein, M is 2,6-diphenyl pyridines or 2,6-double; two (4-tert-butyl-phenyl) pyridines, and L is phenylacetylene or 3,6-di-t-butyl-9-(4-ethynyl phenyl)-9H-carbazole.
As preferably, in the formula of described trivalent gold complex, M is 2,6-double; two (4-tert-butyl-phenyl) pyridines, and L is phenylacetylene.
The structural formula of described trivalent gold complex has following four:
Coordination compound 1
Coordination compound 2
Coordination compound 3
Coordination compound 4
The preparation method of described trivalent gold complex: chlorine gold (III) presoma and L are dissolved in the mixed solution being made up of Hydro-Giene (Water Science)., dichloromethane and triethylamine, 6-12h is stirred under room temperature, after reaction terminates, product is purified and obtains trivalent gold complex;
Described chlorine gold (III) presoma be [Au (C^N^C) Cl] or [Au (tBuC^N^CtBu)Cl]��
The mol ratio of described chlorine gold (III) presoma and L is 2:3-5.
In described mixed solution, it is preferable that the mol ratio of Hydro-Giene (Water Science)., dichloromethane and triethylamine is 1:5460:14.
Described method of purification is: after the solvent of product is spin-dried in silicagel column with volume ratio be 2:1 normal hexane and dichloromethane carry out chromatographic isolation for eluant, then through recrystallization process.
The application in photo catalytic reduction water hydrogen manufacturing of the above-mentioned trivalent gold complex, the trivalent gold complex gram of the present invention participates in photo catalytic reduction water hydrogen manufacturing as photosensitizer, it have been reported that some photosensitizer realizes the method that visible light photocatalytic reduction of water prepares hydrogen in prior art, the present invention can adopt the method for these existing photo catalytic reduction water, and simply trivalent gold complex of the present invention instead of the photosensitizer of prior art. Can be such as, by trivalent gold complex, dichloro three (2,2'-bis-pyridine) cobalt or three (4,4'-di-t-butyl-2,2'-bis-pyridine) rhodium, triethanolamine (TEOA), adding in acetone/water (v/v=4:1) mixed solution, adjust pH to 8.0 with hydrochloric acid, under the irradiation of visible ray, photo catalytic reduction water prepares hydrogen. Described trivalent gold complex is photosensitizer, and TEOA is sacrifice agent, and dichloro three (2,2'-bis-pyridine) cobalt or three (4,4'-di-t-butyl-2,2'-bis-pyridine) rhodium are as reductive water catalyst. The consumption of TEOA, dichloro three (2,2'-bis-pyridine) cobalt or three (4,4'-di-t-butyl-2,2'-two pyridine) rhodium is prior art.
Beneficial effect: the invention provides a series of trivalent gold complex, it is possible to hydrogen is prepared in visible light catalytic reduction in the mixed solution of acetone and water.
Accompanying drawing explanation
Fig. 1 is the H spectrogram of the trivalent gold complex of embodiment 1;
Fig. 2 is the H spectrogram of the trivalent gold complex of embodiment 2;
Fig. 3 is the H spectrogram of the trivalent gold complex of embodiment 3;
Fig. 4 is the H spectrogram of the trivalent gold complex of embodiment 4;
Fig. 5 is the hydrogen output figure that the trivalent gold complex of embodiment 1-4 prepares hydrogen for photo catalytic reduction water.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
0.43mmol [Au (C^N^C) Cl] and 0.1ml phenylacetylene (mol ratio is 1:2) are dissolved in and by 20mg Hydro-Giene (Water Science)., 35mL dichloromethane and 2mL triethylamine mol ratio are: in the mixed solution that 1:5460:14 forms, 6h is stirred under room temperature, after reaction terminates, after solvent is spin-dried in silicagel column with volume ratio be 2:1 normal hexane and dichloromethane carry out chromatographic isolation for eluant, obtain trivalent gold complex through recrystallization process.
Trivalent gold complex is carried out nuclear magnetic resonance, NMR (H spectrogram is shown in Fig. 1), records:1HNMR (DMSO, 500MHz): �� 8.16 (1H, t, J=8.0), 7.98 (2H, d, J=8.0), 7.90 (4H, t, J=6.0), 7.54 (2H, d, J=7.3), 7.41 (4H, m), 7.33 (3H, m). elementary analysis, value of calculation: C25H16NAu:C, 56.94; H, 3.06; N, 2.66. value of calculation: C, 56.66; H, 3.07; N, 2.67.ESI-MS (methanol): measured value: 1076.83 [2 �� M+Na]+. value of calculation: 527.37.
Embodiment 2
By 0.52mmol [Au (C^N^C) Cl] and 0.79ml3,6-di-t-butyl-9-(4-ethynyl phenyl)-9H-carbazole mol ratio is that 2:3 is dissolved in the mixed solution being made up of 20mg Hydro-Giene (Water Science)., 35mL dichloromethane and 2mL triethylamine, 8h is stirred under room temperature, after reaction terminates, after solvent is spin-dried in silicagel column with volume ratio be 2:1 normal hexane and dichloromethane carry out chromatographic isolation for eluant, obtain trivalent gold complex through recrystallization process.
Trivalent gold complex is carried out nuclear magnetic resonance, NMR (H spectrogram is shown in Fig. 2), records:1HNMR (DMSO, 500MHz): �� 8.31 (2H, s), 8.20 (1H, s), 7.99 (4H, t, J=9.2), 7.94 (2H, s), 7.80 (2H, d, J=7.6), 7.62 (2H, d, J=7.9), 7.52 (2H, d, J=7.9), 7.46 (2H, s), 7.38 (4H, m), 1.44 (16H, s). elementary analysis, value of calculation: C46H39NAu:C, 68.74; H, 5.02; N, 1.74. measured value: C, 68.48; H, 5.14; N, 1.67.ESIMS (methanol): measured value: 1632.08 [2 �� M+Na]+. value of calculation: 804.77.
Embodiment 3
By 0.1mL phenylacetylene and 0.43mmol [Au (C^N^C) Cl], 0.38mmol [Au (tBuC^N^CtBu) Cl] (mol ratio is 2:5) join in the mixed solution being made up of 20mg Hydro-Giene (Water Science)., 35mL dichloromethane and 2mL triethylamine, 6h is stirred under room temperature, after reaction terminates, after solvent is spin-dried in silicagel column with volume ratio be 2:1 normal hexane and dichloromethane carry out chromatographic isolation for eluant, obtain trivalent gold complex through recrystallization process.
Trivalent gold complex is carried out nuclear magnetic resonance, NMR (H spectrogram is shown in Fig. 3), records:1HNMR (DMSO, 500MHz): �� 8.10 (1H, t, J=8.0), 8.04 (2H, d, J=1.5), 7.86 (2H, d, J=8.0), 7.81 (2H, d, J=8.2), 7.49 (2H, d, J=7.3), 7.42 (2H, t, J=7.5), 7.35 (3H, m), 1.34 (18H, s). elementary analysis, value of calculation: C33H32NAu:C, 61.97; H, 5.04; N, 2.19. measured value: C, 61.86; H, 5.12; N, 2.26.ESI-MS (methanol): measured value: 1301.77 [2 �� M+Na]+. value of calculation: 639.58.
Embodiment 4
By 0.38mmol [Au (tBuC^N^CtBu) Cl] and 0.57mmol3,6-di-t-butyl-9-(4-ethynyl phenyl)-9H-carbazole (mol ratio is 2:3) joins in the mixed solution being made up of 20mg Hydro-Giene (Water Science)., 35mL dichloromethane and 2mL triethylamine, 10h is stirred under room temperature, after reaction terminates, after solvent is spin-dried in silicagel column with volume ratio be 2:1 normal hexane and dichloromethane carry out chromatographic isolation for eluant, obtain trivalent gold complex through recrystallization process.
Trivalent gold complex is carried out nuclear magnetic resonance, NMR (H spectrogram is shown in Fig. 4), records:1HNMR (DMSO, 500MHz): �� 8.31 (2H, s), 8.14 (1H, t, J=8.0), 8.10 (2H, s), 7.92 (2H, d, J=8.0), 7.85 (2H, d, J=8.2), 7.76 (2H, d, J=8.2), 7.68 (2H, d, J=8.3), 7.52 (2H, d, J=8.5), 7.39 (4H, m), 1.44 (18H, s), 1.37 (16H, s). elementary analysis, value of calculation: C54H55NAu:C, 70.81; H, 6.16; N, 1.53. measured value: C, 70.75; H, 6.19; N, 1.48.ESI-MS (methanol): measured value 879.58 [M-tBu+Na]+. value of calculation: 916.98.
Application testing
Four kinds of trivalent gold complexs that above-described embodiment prepares are respectively used to photo catalytic reduction water and prepare hydrogen, method of testing is: join containing 0.33mM dichloro three (2 by 40 ��m of ol trivalent gold complexs, 2'-bis-pyridine) cobalt, in the mixed solution of the alkaline acetone/water (v/v=4:1) of 0.19M triethanolamine (100mL), after the evacuating air in reactor, (�� > 420nm) is irradiated under the xenon lamp of 300W, the hydrogen that reaction generates is through chromatogram ration analysis, and test result is shown in Fig. 5.
As seen from Figure 5, coordination compound 1,2,3,4 place system generates amount respectively 788 ��m of ol, 516 ��m of ol, 1266 ��m of ol, 1717 ��m of ol of hydrogen after 24 hours in illumination, it can be seen that the hydrogen output of coordination compound 3 is the highest.
Claims (6)
1. a trivalent gold complex, it is characterised in that its chemical general formula is MAuL, wherein, M is 2,6-diphenyl pyridines or 2, double; two (4-tert-butyl-phenyl) pyridine of 6-, L is phenylacetylene or 3,6-di-t-butyl-9-(4-ethynyl phenyl)-9H-carbazole.
2. trivalent gold complex as claimed in claim 1, it is characterised in that in the formula of described trivalent gold complex, M is 2,6-double; two (4-tert-butyl-phenyl) pyridines, and L is phenylacetylene.
3. the preparation method of trivalent gold complex described in claim 1 or 2, it is characterized in that, chlorine gold (III) presoma and L are dissolved in the mixed solution being made up of Hydro-Giene (Water Science)., dichloromethane and triethylamine, 6-12h is stirred under room temperature, after reaction terminates, product is purified and obtains trivalent gold complex;
Described chlorine gold (III) presoma be [Au (C^N^C) Cl] or [Au (tBuC^N^CtBu) Cl];
The mol ratio of described chlorine gold (III) presoma and L is 2:3-5.
4. the preparation method of trivalent gold complex as claimed in claim 3, it is characterised in that in described mixed solution, Hydro-Giene (Water Science)., dichloromethane and triethylamine mol ratio are 1:5460:14.
5. the preparation method of trivalent gold complex as claimed in claim 3, it is characterized in that, described method of purification is: after the solvent of product is spin-dried in silicagel column with volume ratio be 2:1 normal hexane and dichloromethane carry out chromatographic isolation for eluant, then through recrystallization process.
6. the application in photo catalytic reduction water hydrogen manufacturing of the trivalent gold complex described in claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610042077.4A CN105646551B (en) | 2016-01-21 | 2016-01-21 | Trivalent gold complex and its application in photo catalytic reduction water hydrogen manufacturing |
Applications Claiming Priority (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107868095A (en) * | 2016-09-28 | 2018-04-03 | 香港理工大学深圳研究院 | Chiral trivalent gold complex and its preparation method and application |
| CN110088228A (en) * | 2016-10-04 | 2019-08-02 | 香港大学 | Luminescent gold (III) compound containing Cyclometalated tridentate ligand and its preparation for organic light emitting apparatus with aryl assistant ligand |
| JP2022519435A (en) * | 2018-12-21 | 2022-03-24 | 四川知本快車創新科技研究院有限公司 | Alkynyl gold (III) complex and light emitting device |
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| CN101098946A (en) * | 2004-10-29 | 2008-01-02 | 港大科桥有限公司 | Luminescent gold(iii) compounds, their preparation, and light-emitting devices containing same |
| US20090278453A1 (en) * | 2004-10-29 | 2009-11-12 | Vivian Wing-Wah Yam | Luminescent gold(iii) compounds for organic light-emitting devices and their preparation |
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| CN101098946A (en) * | 2004-10-29 | 2008-01-02 | 港大科桥有限公司 | Luminescent gold(iii) compounds, their preparation, and light-emitting devices containing same |
| US20090278453A1 (en) * | 2004-10-29 | 2009-11-12 | Vivian Wing-Wah Yam | Luminescent gold(iii) compounds for organic light-emitting devices and their preparation |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868095A (en) * | 2016-09-28 | 2018-04-03 | 香港理工大学深圳研究院 | Chiral trivalent gold complex and its preparation method and application |
| CN107868095B (en) * | 2016-09-28 | 2020-06-05 | 香港理工大学深圳研究院 | Chiral trivalent gold complex and preparation method and application thereof |
| CN110088228A (en) * | 2016-10-04 | 2019-08-02 | 香港大学 | Luminescent gold (III) compound containing Cyclometalated tridentate ligand and its preparation for organic light emitting apparatus with aryl assistant ligand |
| CN110088228B (en) * | 2016-10-04 | 2023-08-15 | 香港大学 | Luminescent gold (III) compounds containing cyclometallated tridentate ligands with aryl auxiliary ligands for organic light emitting devices and preparation thereof |
| JP2022519435A (en) * | 2018-12-21 | 2022-03-24 | 四川知本快車創新科技研究院有限公司 | Alkynyl gold (III) complex and light emitting device |
| JP7190215B2 (en) | 2018-12-21 | 2022-12-15 | 四川知本快車創新科技研究院有限公司 | Alkynyl gold(III) complex and light-emitting device |
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